Cracking oil with synthetic catalytic compositions



Patented Mar- 3, 1942 I I UNITED STATES PATENT OFFICE 'caacxmo on. wrrn srivrnaric oamnmc courosmoss Gerald G. Connolly, Baton Rouge, 1a., auignor to 8 Oil Development Company, a corporation of Delaware No Drawing. Application December 8, 1938,

.2 Claims. (Cl. 196-52) This invention deals with the use of superior of 23 B. sulfuric acid solution containing aluactivated synthetic gel catalysts and especially minum sulfate equivalent to one mole of A1203, to to the use of such catalysts for the catalytic an equal volume of 25 Be. sodium silicate solucracking of hydrocarbons such as those occurring tion. After the hydrogel has set, it is washed in with distilled water.

relates to the use of certain elements of group IV Impregnated gels having molal ratios of about of the periodic table, for improving the catalytic 12Si0=zlAl=O= are prepared by soaking washed cracking activity of various synthetic gel catalytic silica hydrogel overnight in 'a solution of n a a A1(NO3)L9H20, draining, drying. and de ompos- Certain metal compounds such as silica and 10 ing the aluminum nitrate by heat. These dried alumina have the property of existing in the hy-i products of hydrogel which no longer retain their drogel form, which, upon drying, yields a very spongy characteristics are known as dried gels. porous mass (dried gel), of high catalytic activity. The present invention is specifically concerned din'erent hydrogels may be intimately mixed to the approximate limits of 90-233. Since regenobtain a mechanical mixture (mixed gel), which eration of these catalysts is carried out at high upon rying, may have superior properties over 20 temperatures, it is essential that the oxides be either one of the individual constituents. Plural substantially infusible under such conditions. hydrogeis are obtained by allowing a mixed hy- Furthermore, it has been found that elements drosol of different metal compounds to set. in this group having atomic weightsbelow 90,

Impregnated gels may be prepared by soaking suchias titanium, show detrimental efiects even washed hydrogels in difl'erent salt solutions so in small concentrations, as evidenced by low that the latter are completely dispersed throughyields of gasoline obtained during the cracking out the mass. Gelatinous precipitates differ from operations. The elements with which this inhydrogels by the factthat they separate from vention deals are specifically zirconium, tin and the liquor as a slimy fluid Jelly in a separate thorium, and they are preferably added in the phase leaving some supernatant liquid above. A 3 form of their water soluble salts to the gel cataheterogeneous gel, on the other hand, is a gelati-' lysts. They may be incorporated in the hydrosol nous precipitate dispersed in a hydrosol and alor heterogeneous gel stages, or employed-as mixed lowed to "set" or "gel." hydrous gels or used for impregnating the Ear the purposes of this invention, the term hydrous .or dried gels. The amount of these ele- "hydrous oxide jelly" will be employedlto desig- 3 ments added to these catalysts is very small, prefhate, all gels other than those in the dried form erably not over about 0.5% to 1% or 1.5%, since the flexible characterit has been found that higher amounts detristics attributable to gels containing appreciable mentally affect the activity of the gel catalysts. amounts of imbibed water. Although silica-alumina gels are preferred as For example, a hydrosol of silica may be pre- 40 base stocks, the invention is not limited to this and by mixing equal volumes of 25 36. sodium material but is applicable to other hydrous oxide ilicate solution and 23 Be. sulfuric acid solugels g some catalytic activity. ion. In 3-5 hours, the hydrosol sets to a silica In the preferred procedure, it is desirable to iydrogel, imbibing all of the reaction liquids. employ co-impregnated silica hydrogels obtained The hydrogel may be broken up, washed free of by soaking the purified silica hydrogel produced eaction salts, formed if desired and dried. in known manner in a mixed solution of a soluble J:(S0i):.l8HiO dissolved in liters ,of waternitrate) of the metal promoter desired. The re- 1th 100 liters mission, and washing by desuiting product is drained, dried, decomposed by mtation with"distilled water.. A mechanical heating, and ground or formed, if desired.

iixture of the two hydrogels is btained by in- It has been found that'although alumina-silica mate mixing of the two washed hydrogels. gels are fairly active catalysts for cracking re- Plural hydrogels" of silica and alumina in the actions, their cracking activity can be apprec itio of 12:! may be prepared by adding a volume ably improved by the addition of small amounts of these promoters, which comprise salts of zirconium, tin or thorium, or mixtures thereof.

The invention can be more clearly understood by reference to the following examples, which,

however, are not intended to limit the invention 0 gasoline obtained was 50% by volume. The liquid 15 product had an A. P. I. gravity of 46.9 and the rejected gas obtained amounted to 11.6 liters per hundred grams of liquid product, the gas density being 0.98.

Example 2.-'I'he same silica hydrogel as that 20 described in Example 1 was impregnated with a mixture of aluminum nitrate and zirconium nitrate so that the resulting dried gel contained about 12.5% A1 0: and 0.1% ZrOa. The apparent density of the catalyst was 0.575. Upon crack- 20 ing of the West Texas gas oil under conditions given in Example 1, a gasoline yield of 51% was obtained, and the rejected gas amounted to 0.6 liters per hundred grams of liquid product, showing that the small amount of the zirconium increased somewhat the activity of the cracking catalyst and decreased the gas formation to some extent.

Example 3.-A catalyst was prepared. as in Example 2, except that 1.5% 01 Z10: was present 3 instead of 0.1%. The catalysts apparent density in this case was 0.583.. With this catalyst the gasoline yield obtained was 51.5%. showinga somewhat greater increase in activity by the m further addition of the zirconium promoter.

Example 4.-A co-impregnated silica hydrogel was prepared as in Example 2, except that a tin salt was employed instead of the zirconium'salt.

The catalyst contained 12.5% A120: and 0.1% Upon 4:)

S2102, and its apparent density was 0.629. cracking or the gas oil as in Example 1, the gasoline yield obtained was 54.5% and the amount of rejected gas was 9.7 liters per hundred grams or liquid product, showing adecided improvement in activity over the unpromoted catalyst given in Example 1.

Example 5.-This catalyst was prepared as in Example 4, except that the S1102. content was 1.5% instead of 0.1%. The gasoline yield in this case was 45.5% and the rejected gas amounted to 14.1 liters per hundred grams 0! liquid product, showing a decided drop in activity upon further addition of the tin promoter. v

This gel had a density of 10 Example 6.-The catalyst for this experiment was prepared as in Example 4, except that in this case the S1102 content was 5.0%. With this catalyst the gasoline yield was 36.5% and the amount of rejectedgas was 17 liters per hundred grams of liquid product, showing a much further drop in activity with further addition of the tin promoter.

Example 7.--In this case a catalyst was prepared as in Example 2, except that the promoter was thorium, and the catalyst contained 0.1%

ThOz besides the silica and alumina. When employed for the cracking operation as in Example 1, the gasoline yield obtained with this catalyst was 56.5%, and the amount of rejected gas was 9.4 liters per hundred grams of liquidprodnot, showing a decided increase in yield over that I obtained with the unpromoted catalyst described in Example 1.

Example 8.-Here the catalyst was prepared in the same manner as in Example 7, with the exv ception that the T1102 content was 1.5%. In this case the gasoline yield was 53%, showing a drop in activity when compared to the catalyst containing a lower amount of promoter as in Example 7.

Example 9.-The catalyst for this experiment was also prepared according to Example '7, except that the ThOz content was 5.0%. with this catalyst the gasoline yield was 50%, showing no better activity than the original unpromoted catalyst. v

Although these catalysts operate most satisfactorily when employed for cracking operations. especially in the cracking of petroleum hydrocarbons, they may be advantageously employed for catalyzing other reactions such as dehydrogenation, alkylation, .isomerization, aromatization, polymerization and the like.

Various modifications may be made within the scope oi the present disclosure, and the invention is not limited to any particular examples or theory of operation, but only .by the following claims in which it is intended to cover the invention as broadly as the prior art permits.

1 claim:

1. A method oi cracking hydrocarbon oils which comprises subjecting said oil while at cracking temperature to the action or a synthetic silica-alumina gei catalyst containing a major portion of silica and a minor portion of alumina and a small amount but not more than about 1% of tin oxide and keeping said oil in contact with said catalyst for a period sufilcient to obtain a substantial amount of cracking.

2. The method defined in claim 1, wherein the amount of tin oxide is about 0.1%.

G C. CONNOLLY. 

